Hydrazodicarboxylic aciddihydrazides



United States Patent 3,171,857 HYDRAZODICARBOXYLIC ACIDDIHYDRAZIDESErhard P. Benzing, St. Louis, Mo., assignor to Monsanto Company, acorporation of Delaware No Drawing. Filed Sept. 25, 1961, Ser. No.140,265 Claims priority, application Switzerland, Sept. 27, 1960,10,918/ 60 5 Claims. (Cl. 260554) It has been found thathydrazodicarboxylic aciddihydrazides which have been unknown until noware obtained by reaction of a hydrazodicarboxylic acid diester withhydrazine or a substituted hydrazine.

The hydrazidation proceeds according to the following equation:

In this formula R has the significance usual in such esters and R, R andR are hydrogen atoms or hydrocarbon radicals.

When substituted hydrazines of the formula HNRINRIIRIII are used asreactants in the process of the invention, the R, R" and R radicals arehydrogen or hydrocarbon radicals, except of course one must be ahydrocarbon radical to fit the definition of substituted hydrazine.Usually it is preferred that R, R and R be hydrocarbon radicals of notmore than 18 carbon atoms, more preferably not more than 8 carbon atoms.Illustrative of substituted hydrazines usable in the process of theinvention are the following: Methyl hydrazine, t-butyl hydrazine,n-dodecyl hydrazine, cyclohexyl hydrazine, benzyl hydrazine, phenylhydrazine, p-tolyl hydrazine, [3- naphthyl hydrazine, N,N'-diinethylhydrazine, N,N-diphenyl hydrazine, N,N,N'-trimethyl hydrazine, N-phenyl-N-methyl hydrazine, etc.

The hydrazodicarboxylic acid esters serving as starting material can beprepared in known manner from hydrazine and chloroformic acid esters. Inprinciple, all esters available can be used in this reaction. However,the hydrazidation does not occur equally easily with all esters, as isshown in the following table:

But, these yields which for comparison purposes were obtained withhydrazine by using the working method described in Example 1 do notrepresent the maximum that can be obtained. Esters wherein R is anaraliphatic or cycloaliphatic radical, e.g. the benzyl radical or thecyclohexyl radical, can also be used. Usually it is preferred that Rcontain not more than 18 carbon atoms, and more preferably not more than8 carbon atoms. In general, the methyl ester owing to its price andtechnical availability is preferred in carrying out the invention.

The reaction of an optional hydrazodicarboxylic acid diester is besteilected by heating a mixture of hydrazine and ester for some time athigher temperature. Using hydrazine or aliphatically substitutedhydrazines, the reaction is complete at about 100 C. in most cases after3040 minutes. However, the hydrazidation also occurs at room temperaturewhen the reaction mixture is left standing for a prolonged time. Theless basic aromatical- 1y substituted hydrazines need more prolongedreaction time and possibly a higher reaction temperature. The

3,171,857 Patented Mar. 2, 1965 process of invention can be carried outwith or without a solvent. The lower aliphatic alcohols are especiallysuitable as solvents. A lower aliphatic alcohol is one having from 1 to6 carbon atoms. In general, the same or similar working methods areapplicable as with the amidation of carboxylic acids by using estersthereof.

To supplement the compound of the invention of the examples thefollowing compounds are named as illustrative of compounds of theinvention: hydrazodicarboxylic acid bis-(trimethyl-hydrazide),hydrazodicarboxylic acid bis-(tribenzylhydrazide), hydrazodicarboxylicacid bis (tricyclohexylhydrazide), hydrazodicarboxylic acidbis-(tri-n-dodecylhydrazide), hydrazodicarboxylic acidbis-(N-phenyl-N-methyl-N-ethyl-hydrazide), etc.

The hydrazodicarboxylic acid-dihydrazides of the invention are useful asreducing agents. They also have similar uses to hydrazine. Unlikehydrazine the compounds of the invention are solid and more stable. Theyare useful as solid rocket propellants, since on oxidation large volumesof nitrogen as well as water are formed.

Hydrazodicarboxylic acid-dihydrazides are valuable intermediates. Thecompound obtained with hydrazine reacts with ketones and aldehydes inthe same way as semicarbazide, thereby two molecules of the carbonylcompound can be condensed with one molecule of hydrazodicarboxylicacid-dihydrazide. Derivatives of acetone, ben zaldehyde,isobutyraldehyde, etc., are formed very easily and practicallyquantitatively on mixing the reactants in warm water. The novelcompounds, as long as they contain a replaceable hydrogen atom, can bereacted with carboxylic acid chlorides or anhydrides in the normalmanner, thus obtaining, the corresponding mono, di or evenpolyacylderivative. With for example two equivalents of benzenesulfonylchloride, one obtains the symmetrical dibenzenesulfonylderivative.

Example 1 7.5 g. of hydrazodicarboxylic acid-dimethylester (0.05 mole)and 10 g. of hydrazine hydrate (0.2 mole) are heated at C. for /2 hour.Crystals separate on cooling and standing for some time. These arefiltered off, washed with water and methyl alcohol and dried.Recrystallization from hot water gives pure hydrazodicarboxylicacid-dihydrazide.

Yield 70%; MP. 203205 C.

Analysis.C H N O I Percent C calcd., 16.22; found, 16.34 Percent Hcalcd., 5.44; found, 5.41 Percent N calcd., 56.74; found, 56.72

Example 2 60.8 g. of hydrazine hydrate (1.2 moles) are dissolved in m1.of ethyl alcohol. 81.6 g. of hydrazodicarboxylic acid-diphenylester (0.3mole) are slowly added with stirring. The reaction mixture issubsequently refluxed for /2 hour, then cooled and the precipitatedcrystals filtered 01f.

Yield 40.4 g. (=91% of the theory); M.P. 203-2o5 c.

Hydrazodicarboxylic acid-dihydrazide is insoluble in most commonsolvents but soluble in hot water. The aqueous solution is weaklyalkaline (pH 7-8). Two baseequivalents can be titrated with perchloricacid in acetic acid solution. The aqueous solution displays strongreducing properties.

Example 3 To a 10% solution of hydrazide in warm water a correspondingamount of acetone is added. Crystallization begins at once. The reactionmixture is kept at 50 C. for 15 minutes, then cooled and filtered.

Yield 95%. Recrystallization from acetonitrile, M.P. 234-235 C.

3 Analysis.C H N O (228.3)

Percent C calcd., 42.09; found, 42.16 Percent H calcd., 7.07; found,7.31 Percent N ca1cd., 36.82; found, 36.97

Example 4 Isobutyraldehyde is used instead of acetone and one thenproceeds as in Example 3.

Yield (crude) 100%. Recrystallization from DMF/ water, M.P. 199200 C.

AlZalySl S.'C10H20N 02 Percent C calcd., 46.82; found, 46.91

Percent H calcd., 7.87; found, 7.98 Percent N calcd., 32.79; found,32.61

Example 5 Benzaldehyde is used instead of acetone and one then proceedsas in Example 3.

Yield 52.4% from pyridine/water. from DMF, M.P. 234-235 C.

Analysis.C H N O (324.3)

Percent N calcd., 25.91; found, 25.23.

Example 6 0.88 g. of sodium hydroxide (0.022 mole) and 1.48 g. ofhydrazodicarboxylic acid-dihydrazide (0.01 mole) are successivelydissolved in 10 ml. of water. Then, 2.56 g. of benzenesulfonylchloride(0.02 mole) are added and the mixture is shaken vigorously. The reactionis started by immersing the flask briefly in hot water; it then proceedsexothermally. After minutes shaking it is left standing for 3 hours. Thecrystals are filtered off and washed with water. Recrystallization from50% ethyl alcohol.

Yield 0.65 g. (:15% of the theory); MP. 234236 C.

Analysis.C H N O S (428.5):

Percent C calcd., 39.25; found, 39.14 Percent H calcd., 3.76; found,3.98 Percent N calcd., 19.62; found, 19.41 Percent S calcd., 14.97;found, 14.88

This compound of the invention has the structure @somrmno ONHNHC ONHNHSo@ and it kills nematodes at concentrations as low as 10 p.p.m. If, inExample 6, instead of benzenesulfonylchloride, an equimolar amount ofp-toluene-sulfonylchloride, 2,4-

Recrystallization SO2NHNHO ONHNHC ONHNHSO )n )n wherein Y is a halogenatom, preferably chlorine, or a methyl group, and n is an integer from010 5 inclusive. Y, if there is more than one Y on a phenyl radical, canbe a mixture of halogens and methyl groups.

What is claimed is: 1. A compound of the formula SOzNHNHC ONHNHC ONHNHSO)n (Y)n wherein Y is selected from the class consisting of halogen atomsand the methyl radical, and n is an integer from 0 to 5, inclusive.

@sozmmno ONHNHC ONHNHS o 3. A compound of the formula R (R'C=NNHCONHNHCONHN=C (R' R wherein R is alkyl having not more than 8carbon atoms and R is selected from the class consisting of hydrogenatoms and the methyl radical.

4. (CH C=NNHCONHNHCONHN=C(CH (CH CHCH=NNHCONHNHCONHN =CHCH(CH ReferencesCited in the file of this patent Stolle: Chem. Berichte, volume 43(1910), pages 2468-70.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,l7l,857 March 2, 1965 Erhard P: Benzing It is hereby certified that errorappears in the above numbered paten't reqiiring correction and that thesa id Letters Patent should read as corrected, below Column 4, line 33,beginning with "3 a A compound of" strike out all to and including"=CHCH(CH in line 43, same column 4; in the heading to the printedspecification, line 8, for "5 Claims read 2 Claims H i Signed and sealedthis 24th day of August 19 650 (SEAL) Attest:

-ERNEST W. SWIDER EDWARD J. BRENNER -All.0sting Officer Commissioner ofPatents UNITED STATES PATENT OFFICE I CERTIFICATE F fifl REQTEQN PatentNo. 5,171,857

March 2, 1965 Erhard Pa Benzin It is hereby certified that error appearsthe above numbered patent reqiiring correction and that the sa idLetters Patent should read as oorrectedbelow.

Column 4,

line 33, beginning with "5.; strike out all to and including "=CHCH(CHcolumn 4; in the headin for "5 Claims." read A compound of" J in line43, same g to the printed specification, ,line- 8,

Z Claimsc Signed and sealed this 24th day of August 1965- e (SEAL)Attest:

ERNEST W. SWIDER Ailcsting Officer EDWARD J. BRENNER Commissioner ofPatents

1. A COMPOUND OF THE FORMULA